Crystal laser material



ENERGY OUTPUT (JOULES) April 7, 1970:; R. MAZELSKY A 3,505,239

CRYSTALLASER MATERIAL Filed July 26, 1966 2 Sheets-Sheet z FLUORESCENCE INTENSITY 8 8 8 0 M; l l l I WAVELENGTH, n m

l I J ENERGY INPUT (JOULES) FIG.4

United States Patent 3,505,239 CRYSTAL LASER MATERIAL Robert Mazelsky, Monroeville, and Robert C. Ohlmaun,

Churchill, Pittsburgh, Pa., assignors to Westinghouse Electric Corporation, Pittsburgh, Pa., a corporation of Pennsylvania Filed July 26, 1966, Ser. No. 567,918 Int. Cl. C09k 1/04 US. Cl. 252-301.4 14 Claims ABSTRACT OF THE DISCLOSURE A crystal laser material composed of calcium fluorapatite and doped with neodymium as a partial substitute for calcium therein. Other elements such as selected rare earths, manganese, and charge compensators may also be substituted.

This invention relates to a crystal laser material and more particularly it pertains to an alkaline earth halophosphate crystal doped with a rare earth element, with or without other dopants and charge compensators.

The use of neodymium as a dopant in a number of crystal lattice materials, to obtain laser action having oscillation at optical or near-optical frequencies is well known. Neodymium associated with chormium is used in yttrium aluminum garnet, lanthanum aluminum oxide, and gadolinium oxides. However, these neodymium-doped crystals, such as yttrium aluminum garnet (commonly referred to as YAGzNd) have not been completely satisfactory for use in low-thresold pulse of continuous wave laser operation.

Likewise, other desirable charcteristics of a laser crystal such as low threshold power, high gain, and optical transparency to pumping and laser wavelengths, are not all obtained concurrently with high efliciency in those pn'or known laser materials. Accordingly, there is a critical limitation on the efliciency of optically pumping solid laser as well as on obtaining continuous wave operation.

In accordance with this invention, it has been found that some of the foregoing disadvantages may be overcome by providing a host fluorapatite material which is doped with neodymium or any other rare earth metal having a partially filled 4 electronic shell as a partial substitute for calcium. Such host material when doped with neodymium has a high gain and a lower threshold which exceeds the best existing materials.

Accordingly, it is a general object of this invention to provide a crystal laser material having low pulse threshold and which is suitable for continuous wave laser operation.

It is another object of this invention to provide a crystal laser material having a high gain and higher efliciencies than prior known host materials.

Finally, it is an object of this invention to satisfy the foregoing objects and desiderata in a sample and expedient manner.

Briefly, the present invention involves a crystalline laser material which is composed of calcium fluorapatite (calcium fiuorophosphate) and which is doped with neodymium as a partial substitute for the calcium therein, hereinafter referred to as FAPzNd. Further, as will be disclosed hereinafter, other elements such as selected rare earths, manganese, and charge compensators may be substituted in FAP.

For a better understanding of the invention, reference is made to the drawings, in which:

FIGURE 1 is a perspective view, partly broken away, of an apparatus using a laser rod; 4

FIG. 2 is a graph showing the fluorescence intensity versus wavelength of the emission of neodymium in fluorapatite and in yttrium aluminum garnet;

FIG. 3 is a graph of the fluorescence intensity versus wavelength of the emission of manganese ions and of neodymium absorption in fluorapatite at room temperature; and

FIG. 4 is a graph of energy output versus energy input of fluorapatite doped with varying amounts of neo dymium and of yttrium aluminum garnet doped with neodymium.

There is illustrated a laser in FIG. 1, wherein a rodshaped crystal 10 is disposed within a cylindrical light filter 12 which in turn is mounted within a cylindrical reflector 14. An elongated power supply lamp 16 is mounted within the cylinder 14, the lamp 16 being substantially parallel with the crystal 10. Opposite ends of the cylinder 14 are closed by end panels 18 and 20.

The crystal 10, the tube 12, and the lamp 16 are substantially coextensive with the length of cylinder 14 and extend between the opposite end panels 18 and 20. The lamp 16 is provided with lead wires 22 extending from opposite ends thereof to a suitable power supply which is not shown. As an example, the lamp 16 is a xenon-filled flash lamp of mm. arc length, and 5 mm. inside diameter. The light filter 12 may be a glass tube for filtering out selective wave lengths of the pump light such as ultraviolet waves which are detrimental to laser action. Examples of suitable glasses are quartz and borosilicate glass sold under the trademark of Pyrex. The inner surfaces of the cylinder 14 as well as of the end panels 18 and 20 have a reflective aluminized surface 24 such that light emanating from the lamp 16 is reflected to the crystal 10 in a manner shown by the broken lines 26. It is preferred that all light entering the crystal 10 pass through the filter 12.

Each end panel 18 and 20 is provided with an opening 28 which is aligned with the end of the crystal 10. Reflective means are associated with each end of the rod crystal 10, for instance a pair of mirrors 30 and 32 are disposed in alignment with the axis of the crystal 10, the mirror 30 being partialy reflective and partially transmittive and the mirror 32 being totally reflective of laser beams 34 projected from the ends of the crystal 10 to the mirrors. As a result of the partial reflectivity of the mirror 30, some of the beams 34 pass through the mirror as shown at 36. Alternately the ends of rod crystal 10 can be approximately silvered to effect the same result.

In accordance with the present invention, the rodshaped crystal 10 is a single crystal of fiuorapatite Ca (PO F(FAP) which is doped with neodymium. A technique for making the single crystal is that commonly called the Czochralski method and involves the wetting of a seed crystal by the molten FAP salt and slowly crystallizing the salt on the seed as the seed crystal is withdrawn. For fluorapatite, the molten liquid is held in a container of iridium or other non-reactive noble metal or alloy with melting points in excees of 1750 C. The seed crystal, while being pulled, is rotated at from 10 to rpm. and withdrawn from the melt at rates between 1 and 8 mm. per hours. However, pull and rotation rates faster and slower than those indicated may be suitable for growing laser crystals. After a crystal is prepared, it is then ground and polished to the desired dimension to provide a cylindrical rod with its ends polished to optical quality, the ends being precisely parallel to each other, and perpendicular to the rod axis, as is well known.

The laser crystal 10 in accordance with the invention comprises crystalline calcium florophosphate,

which is the mineral fiuorapatite (FAP). Fluorapatite as a host material may be converted to a material capable of the production of laser action by the addition of a dopant to the material, such dopants consisting of ions of the trivalent rare earth 4 type elements including particularly europium, terbium, holmium, thulium, erbium, neodymium, praseodymium, and ytterbium. Neodymium has proven to be outstanding. The addition of neodymium or any other dopant from the group of rear earth elements is made as a substitute for a minor portion of the calcium in fluorapatite.

A crystal of the halophosphate of the apatite structure may be prepared in any feasible manner at an elevated temperature as is indicated by one of the formulas:

2 scaco +6caHPo.+caF

2Ca 3F Reaction (2) is preferred. Intermediate reactions may occur, but the foregoing formulas represent the basic ultimate reactions.

The dopant ion, Nd, is incorporated by replacement of calcium ions in either the phosphate or the fluoride reactants. Thus, Nd O or NdF may be substituted for a part of the CaF or CaCO or combinations thereof in the above reactions. Other neodymium materials such as Nd2(C204)3, Nd2(SO4)3, and Nd2(PO4)3 may b6 used to produce a useful laser crystal.

However, the amount of neodymium need not be added in stoichiometric proportions substituting for calcium so long as the resultant crystal is essentially the apatite structure.

EXAMPLE I A typical weight radio for materials used to prepare a crystal of FAP2Nd is:

These finely divided materials are admixed and melted together at about 1700 C. until completely reacted. A single crystal is pulled by the Czochralski method. The above melt composition contains a nominal neodymium doping of about 2 atom percent but the resultant crystal contains a lower concentration of neodymium (Nd in the typical hexagonal crystal structure of apatite.

In a similar manner the oxide or carbonate of europium, terbium, holrnium, thulium, erbium, praseodymium, and ytterbium can be substituted for a part of or all of the neodymium oxide in Example I.

In general the neodymium doped fluorapatite has the following nominal formula:

where x has a value of from 0.001 to 0.2. For laser use, the optimum value of x is 0.05 to 0.1. For example, where JCT-J06, the formula is Ca4 91Nd Q6(PO)3F- The fluorescence spectra of neodymium in crystals of FAP and YAG are illustrated in FIG. 2. The FAPtNd 0.4% spectrum is characteristic of the spectra for the electric field perpendicular to the c-axis of the crystal (E.Lc). The spectra for EH0 is very similar except that the principal emission line is even more intense (by about 2.5 times) compared to the other lines. The fluorescence spectra of Nd show that in PAP the emission is somewhat unique compared to Nd emission in YAG in that a much larger fraction of the emission is found in a single line. The FAPzNd line is located at 10629; and is about 6 Angstroms wide for EH0. The internal emission efficiency at 1.062% for FAPzNd 0.4% for Ellc is 2.6:03 times greater than that of YAGzNd 1.5% at 1.0648 The YAG:Nd line is 6.5 Angstroms wide and is less intense. Thus, the spectral effieiency at room temperature is about 2.6 times greater for Nd in PAP than in YAG. The stimulated emission gain for a given rate of absorbing energy will be correspondingly greater for PA? than YAG. The bid absorption and excitation spectra are similar for the two materials although the absorption in PAP is somewhat greater than in YAG. For the same cavity losses the continuous Wave threshold of a FAPzNd laser rod should be a maximum of one-third that of the same size YAGzNd rod.

In order to maintain electroneutrality without formation of lattice vacancies an additional element or elements may be added to compensate for the valence difference between calcium and neodymium. Thus, the substitution of a trivalent rare earth ion in a divalent calcium site requires charge compensation by the addition of either a monovalent cation or a divalent anion in the calcium or fluoride sites, respectively. Suitable monovalent ions for every neodymium substitution in a calcium site include at least one of the alkali metals such as lithium, sodium, potassium, and rubidium. The ionic radii of the other metals in the alkali group, namely cesium and francium, are believed to be too large for substitution in the calcium site. Lithium, sodium, potassium, and rubidium is added as a charge compensator for calcium in an amount up to the mole proportion of the neodymium present. Because its ionic size is substantially equal to that of calcium, sodium is the preferred element for substitution to obtain the required charge compensation. The nominal formula for the laser material which is doped with neodymium and charge compensated by monovalent ions is as follows:

x 5-2x x (P04) 3F Where M is lithium, sodium, potassium, and/or rubidium, and x has a value of from 0.001 to 0.2.

The reaction to produce alkali metal compensated FAPzNd is carried out as in Example I. For a sodiumcompensated typical charge for the initial melt, the following is exemplary:

Gms.

CaCO 15.000 CaHPQ; 47.760 4.501 1.939 0.611

When melted and crystallized as in Example I this gives a nominal composition of where x varies from 0.001 to 0.2; the optimum value of x being between 0.05 and 0.1. Oxygen may be convenient- 1y added as Nd O A specific example of a crystal of fluorapatite doped with neodymium and charge compensated with oxygen is:

4.94 .06( 4) a .94 .os

Compensation to maintain electroneutrality in the crystal may occur in other ways, such as by the presence of calcium vacancies or interstitial fluoride ions, which is self compensation. Self compensation of the crystal, however, is undesirable as an alternative to charge compensation where a monovalent ion such as sodium is added to the calcium site or where a divalent anion such as oxygen is added as a partial substitute for the fluorine ion to keep the ionic charges in the crystal in balance. It has been found that where such cations or anions are not added as charged compensators and the crystal is permitted to self compensate by induced vacancies in the lattice, the crystal ultimately develops a color center which reduces the optical properties and overall efficiency of the crystal.

Though calcium is the preferred alkaline earth metal in the PAP, it is understood that other divalent metals including magnesium, strontium, and barium may be used to replace a part or all of the calcium. Table I lists these alkaline earth metals together with their atomic size in angstroms.

From the table, it is evident that magnesium is smaller than calcium 'by 20% for which reason it is difficult to completely substitute magnesium in the calcium site in apatite while retaining all its properties. However, the alkaline earth metals either individually or in combination may be substituted for calcium in varying amounts and still retain the apatite structure. For example, Sr (PO F the apatite crystal structure and is suitable as a laser host material.

In accordance with another aspect of the invention, which is being specifically claimed in a copending application S.N. 583,760, the efiiciency of the laser may be improved by the simultaneous or double doping of fluorapatite with both manganese and neodymium. As shown in FIG. 3, the fluorescence spectrum of manganese overlaps the absorption spectrum of neodymium. Manganese absorbs energy in spectra regions where neodymium does not absorb even though there are some regions where the absorption spectra for both metals are identical Or overlapping. The energy absorbed by manganese may be subsequently transferred to the neodymium ions due to the overlap shown in FIG. 3 and thereby enhance the output energy of these ions.

Manganese can be substituted directly in the calcium site without the use of lattice compensation whereas, the substitution of the trivalent rare earth ion such as neodymium in a divalent calcium site requires charge compensation to maintain electroneutrality. Any combination of the previously discussed compensating means may be employed in a process where neodymium and manganese are employed. For oxygen compensation the following general formula applies to the manganese-neodymium doped crystals:

where y has a value of from 0.0 up to the solubility limit of manganese, and x has a value of from 0.001 to 0.2.

Accordingly, crystals of neodymium doped fluorapatite may be sensitized by incorporating up to mole percent of manganese replacing an equimolar quantity of calcium. Other divalent transition metal ions may also be used to sensitize neodymium doped PAP, and particularly vanadium and titanium, both of which like manganese have a valence of 2 and any one or any two or all three or manganese, vanadium, and titanium may be directly substituted for a part of the calcium.

The use of manganese with neodymium to produce FAP: Mn, Nd may produce a significant improvement in the efiiciency over FAPzNd both in continuous and pulse lasers. Manganese introduces effective pumping bands at wavelengths not absorbed directly by the neodymium. Fluorapatite is an extremely attractive host for manganese sensitization because a high concentration of manganese may be substituted for calcium. Moreover, fluorapatite which is doped with neodymium and manganese may also be charge compensated by both cations and anions. The general formula for such a material is Where x has a value of from 0.001 to 0.2, y has a value of from 0.0 up to the solubility limit of manganese, z has a value of from 0.0 up to the limit of lattice stability, w has a value of from 0.0 to that of x, and M is at least one of the alkaline earth metals selected from the group consisting of lithium, sodium, potassium, and rubidium. The charge neutrality must be maintained, which requires that x=w'+z.

The following example is further illustrative of the present invention:

EXAMPLE II The performance of laser crystals of fluorapatite doped with varying amounts of neodymium (FAPzNd) was compared with that of the presently best known crystal material, i.e. yttrium aluminum garnet doped with neodymium (YAG:Nd). One YAG crystal doped with 1.5 mole percent neodymium having a rod size of 0.25 inch diameter and a length of 1.48 inch was prepared and tested. Likewise, three crystals of PAP doped with neodymium were prepared and tested. One FAP crystal contained approximately 1.3 mole percent neodymium and had a diameter of 0.25 inch and a length of 2.0 inch. The second FAP crystal contained approximately 1.1 mole percent neodymium and had a diameter of 0.178 inch and a length of 1.75 inch. The third FAP crystal contained approximately 1.4 mole percent neodymium, had a diameter of 0.24 inch and a length of 1.73 inch. The parameters and test results of the YAG:Nd crystal and of the three FAPzNd crystals are listed in Table II.

TABLE II.LASER TESTS CONDUCTED WITH ONE YAG:Nd ROD AND THREE FAPINd RODS The gain coefficient per umped energy shows a marked improvement for the FAPzNd crystals over that of the YAG:Nd crystal. Finally, the efficiency of the FAPzNd crystals exceeds that of the YAG:Nd crystal and the results of this test are shown in FIG. 4 where the energy input in joules is plotted against the energy output. In FIG. 4, the maximum slope efiiciency of the YAG:Nd crystal is 1.65 percent which is substantially less than the latest prepared FAPzNd crystal having an efficiency slope of 2.4 percent.

Accordingly, the fluorapatite doped with neodymium is an improvement over prior known laser materials such as yttrium aluminum garnet for decreased laser threshold power, increased gain, and improved efliciency for use in lasers which oscillate at about 1.06 1. wavelength. Moreover, fluorapatite doped with neodymium has 3 to 5 times higher gain than yttrium aluminum garnet doped with neodymium for the same energy absorbed. Thus, it is easier to stimulate laser action in the fluorapatite than in the garnet.

What is claimed is:

1. A crystal suitable for laser application consisting essentially of a host fluorapatite material having the formula Ca (PO F, the material being doped with at least one trivalent rare earth 4 type element selected from the group consisting of europium, terbium, holmium, thulium, erbium, neodymium, praeseodymium, and ytterbium, which is substituted for a minor portion of calcium therein and which material when doped is an active laser material; said material optionally containing a charge compensator ion consisting of at least one member of the group of lithium, sodium, potassium, rubidium which substitutes for a further minor portion of the calcium, and optionally containing oxygen which partially replaces fluorine, and optionally containing at least one divalent metal selected from the group consisting of magnesium, strontium, and barium, as a substitute for up to all of the calcium of said host material.

2. The crystal of claim 1 wherein neodymium is substituted for a minor portion of calcium.

3. The crystal of claim 1 wherein the doped host material has the formula Ca Nd (PO F, where x has a value of from 0.001 to 0.2.

4. The crystal of claim 3 wherein x has a value of from about 0.05 to about 0.1.

5. The crystal of claim 4 wherein x has a value of about 0.06.

6. The crystal of claim 1 wherein the monovalent element, is present as a partial substitute for the calcium in addition to neodymium.

7. The crystal of claim 6 wherein the monovalent element is present substantially equally in moles to neoclymium.

8. The crystal of claim 1 wherein the doped host material has the formula Ca Nd M (PO F, where M is at least one of the monovalent elements and x has a value of from 0.001 to 0.2.

9. The crystal of claim 8 wherein at has a value of about 0.1.

10. The crystal of claim 1 which further includes a charge compensating element in stoichiometric proportions for the neodymium substitutionally replacing one of calcium and fluorine, the charge compensating elements being one of the monovalent elements as a cation substitute for calcium, and of divalent oxygen as an anion substitute for fluorine.

11. The crystal of claim 1 wherein the fluorine ions are partially substituted for by oxygen ions, and having the formula Ca Nd (PO F O where x has a value of from 0.001 to 0.2.

12. The crystal of claim 11 wherein x has the value of about 0.06.

13. The crystal of claim 10 having the formula References Cited UNITED STATES PATENTS 5/1966 De Paolis et al. 5/1966 Geusic 252301.4

TOBIAS E. LEVOW, Primary Examiner R. D. EDMONDS, Assistant Examiner 

